Fluorochemical composition comprising a polyurethane having a fluorochemical oligomer and a hydrophilic segment to impart stain release properties to a substrate

ABSTRACT

The present invention provides a method for preparing a fluorochemical composition comprising polyurethane by reacting: (A) fluorochemical oligomer of formula (I): M f   m M n —Q 1 —T 1  wherein: M f   m M n  represents flurochemical oligomer comprising m units derived from fluorinated monomer and n units derived from fluorine-free monomer and wherein the fluorinated monomers and fluorine-free monomers may be the same or different; m represents a value of 2 to 40; n represents a value of 0 to 20; T 1  is —OH or —NH 2 ; Q 1  and T 1  together represent an organic residue obtained by removing a hydrogen atom from a chain transfer agent that is functionalized with T 1 ; and (B) difunctional compound capable of reacting with an isocyanate and comprising a poly(oxyalkylene) group having 18 to 280 oxyalkylene moieties with (C) diisocyanate or triisocyanate. Substrates treated with the fluorochemical composition prepared according to the method described above, have good stain release properties in particular for oily stains and water based stains such as wine, tea and coffee.

FIELD OF THE INVENTION

The present invention relates to fluorochemical compositions for thetreatment of substrates, in particular fibrous substrates such astextiles to impart stain release properties to those substrates.

BACKGROUND OF THE INVENTION

Fluorochemical compositions for the treatment of substrates such asleather, textiles and paper are well known and are used to impartvarious properties to the substrate such as water and/or oil repellency,waterproofness, stain release, anti-staining etc. For example, U.S. Pat.No. 5,276,175 discloses isocyanate derivatives comprising fluorochemicaloligomers. In particular, the disclosed fluorochemical compositionscomprise fluorinated compounds, wherein the fluorinated compoundcomprises a fluorochemical oligomeric portion, an organic moiety, and agroup that can impart soft hand, stain release, water repellency, or adurable property when the compound is applied to a fibrous substrate,wherein the fluorochemical oligomeric portion is bonded to the organicmoiety through an isocyanate-derived linking group. Substrates sotreated are shown to exhibit particularly durable and abrasion-resistantoil and water repellency. Further, in one of the examples there is showna fluorochemical composition that is based on a condensate of atri-isocyanate, a fluorochemical oligomer and a methoxypolyethyleneoxideglycol. For this composition stain release properties are demonstratedon a polyester/cotton blend fabric.

U.S. Pat. No. 5,350,795 discloses fluorochemical compositions fortreating textile fibers and fabrics to impart oil and water repellencywithout thermal treatment. The compositions comprise an aqueous,substantially organic solvent free, solution or dispersion of (a) afluorochemical acrylate copolymer comprised of a fluorinated acrylatemonomer, polyalkylene glycol acrylate or methacrylate, or polyalkyleneglycol diacrylate or dimethacrylate; and (b) a polyalkoxylatedpolyurethane having pendant perfluoroalkyl groups comprised of analiphatic or aromatic tri- or higher order isocyanate, a fluorinatedalcohol, amine, or mercaptan, and a poly(oxyalkylene) diol or dithiol.

U.S. Pat. No. 4,788,287 and U.S. Pat. No. 4,792,354 disclose a water andoil repellent compound having at least two terminal segments and anintermediate segment connecting the terminal segments that has amolecular weight of from 800 to 20,000. Each terminal segment of thecompound contains at least one polyfluoroalkyl group connected by a—CONH— linking group, the intermediate segment is a urethane oligomercontaining at least two —CONH— linking groups in one molecule, and theterminal segments and intermediate segment are connected by a —CONH—linking group. The urethane oligomer of U.S. Pat. No. 4,792,354 furthercontains a hydrophilic molecular chain.

U.S. Pat. No. 5,491,261 discloses di-, tri- andpoly-perfluoroalkyl-substituted alcohols and acids and derivativesthereof which are prepared from perfluoroalkyl iodides and di-, tri- orpolyalkyl alcohols or acids. They can be reacted with isocyanates, epoxycompounds, anhydrides, acids or acid derivatives to prepare a greatvariety of oil- and water-repellent compositions.

Fluorochemical compositions are also used to facilitate stain or soilrelease from a substrate such as for example a fabric. Routinetreatments of fabrics with modifying additives such as softeners,stiffeners and lubricants to impart desired properties to a commercialfabric typically increase the oleophilicity of the fabric, therebysignificantly increasing its tendency to accept oily stains and reducingits ability to release such stains after laundering. Fluorochemicalcompositions based on a mixture of a fluorinated compound and anon-fluorinated hydrophilic compound or a chemical “hybrid” compoundthat contains fluorochemical oleophobic segments (“F”) andnon-fluorinated hydrophilic segments (“H”) are known to act as stainrelease compositions since they provide oil repellency during normalwear and inhibit wicking or diffusion of oily soils into the fabric orfiber bundles as well as facilitate soil release during laundering.

U.S. Pat. No. 3,574,791 discloses a block-copolymer consisting of F andH segments for use as a stain-release agent. The “F”-segments aresubstantially free of hydrophilic groups whereas the “H” segments aresubstantially free of fluorinated aliphatic groups. It is taught thatdue to this segmentation, the polymer is “autoadaptable”, i.e., a fabrictreated with the polymer will be an oil and water repellent in anatmospheric environment, and when laundered in water, it will becomehydrophilic so stain removal becomes possible. Various possible chemicallinkages are contemplated for connecting the “F” and “H” segments,including a urethane linkage derived from the reaction of an alcohol andan isocyanate.

U.S. Pat. No. 5,509,939 discloses a fluorochemical composition to impartsoil release properties to a substrate. The fluorochemical compositioncomprises urea-linkage-containing-alkoxypolyoxyalkylene fluorocarbamatesprepared by reacting (a) at least one polyisocyanate which contains atleast three isocyanate groups with (b) at least one fluorochemicalreagent which contains one functional group which has at least onehydrogen atom and at least two carbon atoms each of which contains atleast two F atoms, (c) at least one hydrophilic, water-solvable reagentwhich contains a single functional group which has at least one reactivehydrogen atom, (d) at least one reagent which contains one reactivehydrogen and which on reaction with an isocyanate group, yieldsfunctionality which has abeyant chemical reactivity with fibroussubstrates, and then reacting the product with water such that reactants(b), (c) and (d) are reacted with 55% to 95% of the isocyanate groups,and water with the remainder.

Despite the many fluorochemical compositions known to impart stainrelease properties to a substrate, there continues to be a desire forfluorochemical compositions that have improved properties. Desirableproperties for fluorochemical compositions include easy cleanability ofnatural fiber substrates such as cotton and blends of cotton andpolyester, particularly with respect to oil-type stains (dirty motoroil, vegetable oil) and water based stains (tea, coffee); lowmanufacturing cost; high storage stability; easy emulsifiability andhigh performance even if applied in low quantities. It is furtherdesirable that the fluorochemical compositions provide good stainrepellency and oil and/or water repellency properties to the substrate.

SUMMARY OF THE INVENTION

The present invention provides a method for preparing a fluorochemicalcomposition comprising polyurethane by reacting:

(A) fluorochemical oligomer of formula (I)

M^(f) _(m)M_(n)—Q¹—T¹  (I)

wherein:

M^(f) _(m)M_(n) represents a fluorochemical oligomer comprising m unitsderived from fluorinated monomer and n units derived from fluorine-freemonomer and wherein the fluorinated monomers and fluorine free-monomersmay be the same or different;

m represents a value of about 2 to 40;

n represents a value of 0 to about 20;

T¹ is —OH or —NH₂;

Q¹ and T¹ together represent an organic residue obtained by removing ahydrogen atom from a chain transfer agent that is functionalized withT¹; and

(B) difunctional compound capable of reacting with an isocyanate andcomprising a poly(oxyalkylene)group having about 18 to 280 oxyalkylenemoieties; with

(C) diisocyanate or triisocyanate.

The present invention further provides a fluorochemical compositioncomprising a polyurethane obtainable by the above method and the use ofthe fluorochemical composition to provide stain release properties to asubstrate.

In accordance with a further embodiment, there is provided afluorochemical composition comprising: (i) polyurethane obtainable byreacting:

(A) fluorochemical oligomer of formula (I)

M^(f) _(m)M_(n)—Q¹—T¹  (I)

wherein:

M^(f) _(m)M_(n) represents a fluorochemical oligomer comprising m unitsderived from fluorinated monomer and n units derived from fluorine-freemonomer and wherein the fluorinated monomers and fluorine-free monomersmay be the same or different;

m represents a value of about 2 to 40;

n represents a value of 0 to about 20;

T¹ is —OH or —NH₂;

Q¹ and T¹ together represent an organic residue obtained by removing ahydrogen atom from a chain transfer agent that is functionalized withT¹; and

(B) difunctional compound capable of reacting with an isocyanate andcomprising a poly(oxyalkylene)group; with

(C) diisocyanate or triisocyanate; and

(ii) polymer selected from the group consisting of polyvinyl alcohols,copolymers of (meth)acrylic acid, alkyl esters of (meth)acrylic acid,polyethylene glycols and non-ionic cellulose ethers.

Also provided is the use of a fluorochemical composition to impart stainrelease properties to a substrate, said fluorochemical compositioncomprising polyurethane obtainable by reacting:

(A) fluorochemical oligomer of formula (I)

M^(f) _(m)M_(n)—Q¹—T¹  (I)

wherein:

M^(f) _(m)M_(n) represents a fluorochemical oligomer comprising m unitsderived from fluorinated monomer and n units derived from fluorine-freemonomer and wherein the fluorinated monomers and fluorine-free monomersmay be the same or different;

m represents a value of about 2 to 40;

n represents a value of 0 to about 20;

T¹ is —OH or —NH₂;

Q¹ and T¹ together represent the organic residue obtained by removing ahydrogen atom from a chain transfer agent that is functionalized withT¹; and

(B) difunctional compound capable of reacting with an isocyanate andcomprising a poly(oxyalkylene)group; with

(C) diisocyanate or triisocyanate.

Further provided is the treatment of a substrate using one of thefluorochemical compositions described herein and a substrate treatedwith one of said fluorochemical compositions.

DETAILED DESCRIPTION OF THE INVENTION

In connection with the present invention, the term “difunctional”compound means a compound that has only two functional groups capable ofreacting with an isocyanate.

The term “functionalized fluorochemical oligomer” means a fluorochemicaloligomer that contains a functional group capable of reacting with anisocyanate.

The fluorochemical compositions of the present invention can be preparedin a two step reaction. In a first step, a functionalized fluorochemicaloligomer is prepared, which is further reacted to form a polyurethane inthe second step.

In the first step, fluorochemical oligomer according to formula (I) isprepared:

M^(f) _(m)M_(n)—Q¹—T¹  (I)

wherein:

M^(f) _(m)M_(n) represents fluorochemical oligomer comprising m unitsderived from fluorinated monomer and n units derived from fluorine-freemonomer and wherein the fluorinated monomers and fluorine-free monomersmay be the same or different;

m represents a value of about 2 to 40;

n represents a value of 0 to about 20;

T¹ is —OH or —NH₂; and

Q¹ and T¹ together represent the organic residue obtained by removing ahydrogen atom from a chain transfer agent that is functionalized withT¹.

The value of m in the fluorochemical oligomer is between about 2 and 40and preferably between about 2 and 20 and more preferably between about3 and 15. The value of n can be from 0 to about 20 and is preferablybetween about 3 and 10. According to a preferred embodiment, the valueof n is less than that of m. Fluorochemical oligomers derived from twoor more different fluorinated monomers and/or two or more differentfluorine free monomers are within the scope of this invention.

In the above formulas, Q¹ typically represents an organic residueaccording to the following formula:

—S—R—

wherein

R represents an organic divalent linking group that is preferablyselected from the group consisting of linear or branched alkylenes(preferably having about 2 to 6 carbon atoms), cyclic alkylenes,arylenes and aralkylenes.

The fluorochemical oligomer can be prepared by free-radicaloligomerization of fluorochemical monomers (R_(f)—L¹—E) alone or incombination with hydrocarbon monomers (R_(h)—E′), in the presence ofhydroxy- or amino-functionalized chain transfer agents. The term“hydrocarbon”, in connection with the present invention, means anysubstantially fluorine-free organic moiety that contains hydrogen andcarbon and optionally one or more substituents. The aliphatic backboneof the fluorochemical oligomeric portion comprises a sufficient numberof polymerized units to render the portion oligomeric. The aliphaticbackbone preferably comprises from 2 to about 40 polymerized unitsderived from fluorochemical monomers and from 0 to about 20 polymerizedunits derived from hydrocarbon monomers. The R_(n) group in thehydrocarbon monomer is a fluorine-free organic group.

The fluoroaliphatic radical, R_(f), in the fluorochemical monomer, is afluorinated, stable, inert, preferably saturated, non-polar, monovalentaliphatic radical. It can be straight chain, branched chain, cyclic orcombinations thereof. It can contain heteroatoms such as oxygen,divalent or hexavalent sulfur, or nitrogen. R_(f) is preferably afully-fluorinated radical, but hydrogen or chlorine atoms can be presentas substituents if not more than one atom of either is present for everytwo carbon atoms. The R_(f) radical has at least about 3 and up to about18 carbon atoms, preferably about 3 to 14, especially about 6 to 12carbon atoms, and preferably contains about 40% to 80% fluorine byweight, more preferably about 50% to 78% fluorine by weight. Theterminal portion of the R_(f) radical is a perfluorinated moiety, whichwill preferably contain at least 7 fluorine atoms. e.g., CF₃CF₂CF₂—,(CF₃)₂CF—, F₅SCF₂—. The preferred R_(f) radicals are fully orsubstantially fluorinated and are preferably follow the formulaC_(n)F_(2n+1)— where n is about 3 to 18.

The linking group, L¹, links the R_(f) group to the free radicalpolymerizable group E. L¹ preferably contains from 1 to about 20 carbonatoms. L¹ can optionally contain oxygen, nitrogen, or sulfur-containinggroups or a combination thereof, and L¹ is preferably free of functionalgroups that substantially interfere with free-radical oligomerization(e.g., polymerizable olefinic double bonds, thiols, and other suchfunctionality known to those skilled in the art). Examples of suitableL¹ groups include straight chain, branched chain or cyclic alkylene,arylene, aralkylene, oxy, oxo, hydroxy, thio, sulfonyl, sulfoxy, amino,imino, sulfonamido, carboxyamido, carbonyloxy, urethanylene, andureylene groups, and combinations thereof such as sulfonamidoalkylene.Preferred linking groups are selected from the group consisting ofalkylene groups, poly(oxyalkylene) groups having about 1 to 4oxyalkylene moieties and organic divalent linking groups according tothe following formula:

wherein:

R³ represents a linear or branched alkylene group having 2 to 4 carbonatoms, and

R⁴ represents an alkyl group having 1 to 4 carbon atoms.

E and E′ are free radically polymerizable groups that typically containan ethylenically unsaturated group capable of polymerization with itselfor each other. Suitable groups include, for example, moieties derivedfrom vinyl ethers, vinyl esters, allyl esters, vinyl ketones, styrene,vinyl amide, acrylamides, maleates, fumarates, acrylates andmethacrylates. Of these, the esters of alpha, beta unsaturated acids,such as the acrylates and methacrylates are preferred.

Fluorochemical monomers R_(f)—L¹—E as described above and methods forthe preparation thereof are known and disclosed, e.g., in U.S. Pat. No.2,803,615. Examples of such compounds include general classes offluorochemical acrylates, methacrylates, vinyl ethers, and allylcompounds containing fluorinated sulfonamido groups, acrylates ormethacrylates derived from fluorochemical telomer alcohols, acrylates ormethacrylates derived from fluorochemical carboxylic acids, andperfluoroalkyl acrylates or methacrylates as disclosed in EP-A-526 976.

Preferred examples of fluorochemical monomers include:

CF₃(CF₂)₄CH₂OCOC(CH₃)═CH₂

CF₃(CF₂)₆(CH₂)₂OCOC(CH₃)═CH₂

CF₃(CF₂)₆CH₂ ₂OCOCH═CH₂

CF₃(CF₂)₆CH₂OCOC(CH₃)═CH₂

CF₃(CF₂)₆CH₂OCOCH═CH₂

CF₃(CF₂)₇(CH₂)₂OCOCH═CH₂

R=methyl, ethyl or n-butyl

Suitable hydrocarbon monomers R_(h)—E′ are also known and generallycommercially available. Examples of such compounds include the generalclasses of ethylenic compounds capable of free-radical polymerization,such as, for example, allyl esters such as allyl acetate and allylheptanoate; alkyl vinyl ethers or alkyl allyl ethers such as cetyl vinylether, dodecylvinyl ether, 2-chloroethylvinyl ether, ethylvinyl ether;unsaturated acids such as acrylic acid, methacrylic acid, alpha-chloroacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acidand their anhydrides and esters such as vinyl, allyl, methyl, butyl,isobutyl, hexyl, heptyl, 2-ethyl-hexyl, cyclohexyl, lauryl, stearyl,isobornyl or alkoxy ethyl acrylates and methacrylates; alpha-betaunsaturated nitriles such as acrylonitrile, methacrylonitrile,2-chloroacrylonitrile, 2-cyanoethyl acrylate, alkyl cyanoacrylates;alpha, beta-unsaturated carboxylic acid derivatives such as allylalcohol, allyl glycolate, acrylamide, methacrylamide, n-diisopropylacrylamide, diacetoacrylamiide, N,N-diethylaminoethylmethacrylate,N-t-butylamino ethyl methacrylate; styrene and its derivatives such asvinyl toluene, alpha-methylstyrene, alpha-cyanomethyl styrene; lowerolefinic hydrocarbons which contain halogen such as ethylene, propylene,isobutene, 3-chloro-1-isobutene, isoprene, and allyl or vinyl halidessuch as vinyl and vinylidene chloride. Preferred co-monomers which canbe copolymerized with the above-described fluoroaliphaticradical-containing monomers include those selected fromoctadecylmethacrylate, laurylmethacrylate, butylacrylate, N-methylolacrylamide, isobutylmethacrylate, ethylhexyl acrylate, ethylhexylmethacrylate, lycidyl methacrylate, vinylchloride and vinylidenechloride.

The hydroxy- or amino-functionalized chain transfer agents useful in thepreparation of the fluorochemical oligomer preferably correspond to thefollowing formula:

HS—R—X

wherein:

R is as defined herein, and

X is an —OH or —NH₂ moiety.

Examples of chain transfer agents include those selected from2-mercaptoethanol, 3-mercapto-2-butanol, 3-mercapto-2-propanol,3-mercapto-1-propanol and 2-mercapto-ethylamine. A single compound or amixture of different chain transfer agents may be used. A preferredchain transfer agent is 2-mercaptoethanol.

In order to prepare the functionalized fluorochemical oligomer, afree-radical initiator is normally present. Such free-radical initiatorsare known in the art and include azo compounds, such asazobisisobutyronitrile (AIBN) and azobis(2-cyanovaleric acid) and thelike, hydroperoxides such as cumene, t-butyl, and t-amyl hydroperoxide,dialkyl peroxides such as di-t-butyl and dicumylperoxide, peroxyesterssuch as t-butylperbenzoate and di-t-butylperoxy phtalate,diacylperoxides such as benzoyl peroxide and lauroyl peroxide.

In a second step, the fluorochemical oligomer (or mixture offluorochemical oligomers) and the difunctional compound capable ofreacting with an isocyanate group are reacted with a diisocyanate ortriisocyanate, to obtain the polyurethane. The reaction may furtherinvolve an isocyanate blocking agent or a fluorine-free oligomer. Itwill be appreciated by one skilled in the art that the preparation ofpolyurethanes according to the present invention results in a mixture ofcompounds.

If diisocyanate is used, the fluorochemical oligomer is preferably usedin amount sufficient to react with about 9% to 50% of the number ofisocyanate groups, the difunctional compound is preferably used is anamount sufficient to react about 50% to 90% of the isocyanate groups andthe isocyanate blocking agent or fluorine-free oligomer is preferablyused in an amount sufficient to react 0 to about 25% of the isocyanategroups.

In case a triisocyanate or a mixture with a diisocyanate is used, thefluorochemical oligomer is preferably used in amount sufficient to reactwith about 6% to 33% of the number of isocyanate groups, thedifunctional compound is preferably used is an amount to react about 33%to 61% of the isocyanate groups and the isocyanate blocking agent orfluorine-free oligomer is preferably used to react about 25 to 40%, morepreferably about 28% to 33% of the isocyanate groups.

An oxyalkylene moiety in the poly(oxyalkylene) group contained in thedifunctional compound preferably has about 2 to 4 carbon atoms. Examplesof such moieties include —OCH₂—CH₂—, —OCH₂—CH₂—CH₂—, —OCH(CH₃)CH₂—, and—OCH(CH₃)CH(CH₃)—. The oxyalkylene moieties in the poly(oxyalkylene)group can be the same (e.g., poly(oxypropylene)), or present as amixture (e.g., a heteric straight or branched chain or a chain ofrandomly distributed oxyethylene and oxypropylene moieties, or astraight or branched chain of blocks of oxyethylene moieties and blocksof oxypropylene moieties). The backbone of poly(oxyalkylene) groups canbe interrupted by or include one or more catenary linkages. Where thecatenary linkages have three or more valences, they provide a means forobtaining a branched chain of oxyalkylene moieties. Thepoly(oxyalkylene) group contained in the difunctional compoundpreferably contains between about 18 and 280 and more preferably betweenabout 22 and 182 of oxyalkylene units.

Preferred difunctional compounds comprising a poly(oxyalkylene) groupcorrespond to the following formula:

H—W¹—R₆—(O—R₇)_(i)—(O—R⁸)_(j)—W²—H

wherein:

R⁶ represents a linear or branched alkylene having about 1 to 4 carbonatoms;

R⁷ and R⁸ are each independently selected from the group consisting oflinear or branched alkylene groups having 2 to 4 carbon atoms;

W¹ and W² are each independently selected from the group consisting ofO, S and NH;

i and j are each independently selected integers of 0 to 150, providedthe sum of i and j is at least about 8.

Preferably, R⁷ ethylene and R⁸ is linear or branched propylene and theratio of i to j is at least 1 and preferably greater than 1. Mostpreferably, R⁷ is ethylene and j is 0.

Examples of difunctional compounds include polyalkylene glycols (e.g.,polyethylene glycol), a hydroxy-tenninated copolymer (including a blockcopolymer) of ethyleneoxide and propylene oxide, a diamino-terminatedpoly(alkylene oxide), Jeffamines™ ED having a molecular weight between600 and 6000, Jeffamine™ EDR-148 and poly(oxyalkylene) thiols.

Diisocyanate or triisocyanates for use in accordance with the presentinvention include aliphatic and aromatic isocyanates. Examples includearomatic diisocyanates such as 4,4′-methylenediphenylenediisocyanate,4,6-di-(trifluoromethyl)-1,3-benzene diisocyanate,2,4-toluenediisocyanate, 2,6-toluene diisocyanate, o, m, and p-xylylenediisocyanate, 4,4′-diisocyanatodiphenylether,3,3′-dichloro-4,4′-diisocyanatodiphenylmethane,4,5′-diphenyldiisocyanate, 4,4′-diisocyanatodibenzyl,3,3′-dimethoxy-4,4′-diisocyanatodiphenyl,3,3′-dimethyl-4,4′-diisocyanatodiphenyl,2,2′-dichloro-5,5′-dimethoxy-4,4′-diisocyanato diphenyl,1,3-diisocyanatobenzene, 1,2-naphthylene diisocyanate,4-chloro-1,2-naphthylene diisocyanate, 1,3-naphthylene diisocyanate, and1,8-dinitro-2,7-naphthylene diisocyanate; alicyclic diisocyanates suchas 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate;3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate; aliphaticdiisocyanates such as 1,6-hexamethylenediisocyanate,2,2,4-trimethyl-1,6-hexamethylenediisocyanate, and1,2-ethylenediisocyanate; aliphatic triisocyanates such as1,3,6-hexamethylenetriisocyanate; aromatic triisocyanates such aspolymethylenepolyphenylisocyanate (PAPI); cyclic diisocyanates such asisophorone diisocyanate (IPDI) anddicyclohexylmethane-4,4′-diisocyanate.

Also useful are isocyanates containing internal isocyanate-derivedmoieties such as biuret-containing triisocyanates such as that availablefrom Bayer as DESMODUR™ N-100, isocyanurate-containing triisocyanatessuch as that available from Huls AG, Germany, as IPDI-1890, andazetedinedione-containing diisocyanates such as that available fromBayer as DESMODUR™ TT. Also, other diisocyanate or triisocyanates suchas those available from Bayer as DESMODUR™ L and DESMODLTR™ W, andtri-(4-isocyanatophenyl)-methane (available from Bayer as DESMODUR™ R)are suitable.

The fluorine-free oligomer optionally used in the preparation of thepolyurethanes, may be prepared using a procedure similar to thepreparation of the fluorochemical oligomer except that onlyfluorine-free monomers are used. Suitable fluorine-free monomers includethose of the type R_(h)—E′ described above. According to a particularlypreferred embodiment, the fluorine-free oligomer is derived from anoligomerization of at least one monomer that includes a functional groupcapable of cross-linking upon activation for example, by heat. Typicalexamples of such functional groups include blocked isocyanates andalkoxysilane groups. Examples of monomers including a functional groupcapable of cross-linking upon activation include alkoxysilanefunctionalized acrylates or methacrylates or monomers that contain ablocked isocyanate such as the reaction product of2-hydroxy-ethyl-(meth)acrylate, a diisocyanate and an isocyanateblocking agent. The fluorine-free oligomer preferably has apolymerization degree between about 2 and 40 and more preferably betweenabout 3 and 20.

Optionally isocyanate blocking agents may be used in this invention.Such agents include compounds that, upon reaction with a compoundcontaining an isocyanate group, form a compound that is unreactive atroom temperature with an isocyanate-reactive compound but which reactswith isocyanate-reactive compounds at elevated temperatures. Suitableisocyanate blocking agents will typically react with isocyanate-reactivecompounds at a temperature of about 50 to 190° C. Examples of suitableisocyanate blocking agents include aryl alcohols (e.g., phenols,cresols, nitrophenols, o- and p-chlorophenol, napthols,4-hydroxybiphenyl); C₂ to C₈ alkanone oximes (e.g., acetone oxime,butanone oxime); benzophenone oxime; aryl-thiols (e.g., thiophenol);organic carbanion active hydrogen compounds (e.g., diethyl malonate,acetylacetone, ethyl acetoacetate, ethylcyanoacetate) andepsilon-caprolactone. A single compound or a mixture of differentmasking or blocking agents may be used. Particularly preferredisocyanate blocking or masking agents include C₂ to C₈ alkanone oximes,e.g., 2-butanone oxime.

The condensation reaction is carried out under conventional conditionswell-known to those skilled in the art. Preferably the reaction is runin the presence of a catalyst. Suitable catalysts include tin salts suchas dibutyltin dilaurate, stannous octanoate, stannous oleate, tindibutyldi-(2-ethyl hexanoate), stannous chloride; and others known tothose skilled in the art. The amount of catalyst present will depend onthe particular reaction, and thus it is not practical to reciteparticular preferred concentrations. Generally, however, suitablecatalyst concentrations are from about 0.001 percent to 10 percent, andpreferably about 0.1 percent to 5 percent, by weight based on the totalweight of the reactants.

The condensation reaction is preferably carried out under dry conditionsin a polar solvent such as ethyl acetate, acetone, methyl isobutylketone, toluene and the like. Suitable reaction temperatures will beeasily determined by those skilled in the art based on the particularreagents, solvents, and catalysts being used. While it is not practicalto enumerate particular temperatures suitable for all situations,generally suitable temperatures are between about room temperature andabout 120° C.

The fluorochemical composition of this invention can be applied usingconventional application methods but is preferably used as an aqueousemulsion. Alternatively it can be used as a treatment composition insolvent. An aqueous emulsion will generally contain water, an amount offluorochemical composition effective to provide the desired repellentproperties to a substrate treated therewith, and a surfactant in anamount effective to stabilize the emulsion. Water is preferably presentin an amount of about 70 to 2000 parts by weight based on 100 parts byweight of the fluorochemical composition of the invention. Thesurfactant is preferably present in an amount of about 1 to 25 parts byweight, preferably about 2 to 10 parts by weight, based on 100 parts byweight of the fluorochemical composition. Conventional cationic,nonionic, anionic, and zwitterionic surfactants are suitable.

The amount of aqueous or solvent-based treating composition applied to asubstrate should be sufficient to impart high stain release propertiesto the substrate. Typically, an amount of treating compositionsufficient to provide about 0.01% to by weight, preferably about 0.05%to 2% by weight, based on the weight of the substrate, of fluorochemicalcomposition on the treated substrate is adequate. The amount which issufficient to impart desired stain release can be determined empiricallyand can be increased as necessary or desired.

To the fluorochemical composition of the invention there may also beadded other fluorinated products, polymers or auxiliary products such asstarch, dextrin, casein, polyvinyl alcohols, cellulose and cellulosederivatives such as cellulose ethers, copolymers of (meth)acrylic acidand an alkyl (meth)acrylate, polyglycols such polyethylene glycols,sizing agents, materials to improve water and/or oil repellency, fireproofing or antistatic properties, buffering agents, fungicidal agents,optical bleaching agents, sequestering agents, mineral salts,surface-active agents, or swelling agents to promote penetration.Preferably, copolymers of an alkyl(meth)acrylate and (meth)acrylic areused auxiliary products in the fluorochemical composition. Typically,the weight ratio of meth(acrylic) acid to alkyl (meth)acrylate in suchpolymers is between about 20:80 and 90:10, and more preferably isbetween about 50:50 and 85:15. It is further preferred that the alkylgroup of the (meth)acrylate monomer is a lower alkyl group having about1 to 6 carbon atoms. Examples of alkyl (meth)acrylate monomers include,methyl, ethyl and n-butyl acrylates and methacrylates. The copolymer ofan alkyl (meth)acrylate and (meth)acrylic acid may further contain unitsderived from ethylenically unsaturated monomers but preferably thecopolymer only consists of units or moieties derived from alkyl(meth)acrylates and (meth)acrylic acid. The copolymer may also bepartially or fully neutralized with a base such as sodium hydroxide orammonium hydroxide.

Particularly suitable auxiliary products for use in the fluorochemicalcomposition include polyvinyl alcohols and non-ionic cellulose ethers.It has been found that when the fluorochemical composition of theinvention contains at least a polyvinyl alcohol or a non-ionic celluloseether, the ability to release stains can be substantially improvedrelative to a fluorochemical composition that does not include theseauxiliary products. Examples of non-ionic cellulose ether derivativesinclude methyl cellulose, hydroxypropyl cellulose andmethylhydroxypropyl cellulose. Preferably, the etherified cellulose ishighly hydrophilic. Accordingly, cellulose ethers that contain largehydrophobic substituents such as the hydrophobically modified celluloseether (available under the tradename NEXTON™ from Aqualon) are notpreferred for use in the fluorochemical composition of this invention. Asubstantial improvement was noticed for many fluorochemical compositionsthat contain polyvinyl alcohol or a non-ionic cellulose ether, relativeto releasing dirty motor oil stains, while a less pronounced improvementhas been observed for the release of tea or wine stains. This finding israther surprising since the addition of other hydrophilic polymers, suchas ionic cellulose ethers, did not show this improvement and evenreduced the stain release performance of certain fluorochemicalcomposition.

The substrates treated by the fluorochemical composition of thisinvention are not especially limited and include plastic, metal, glass,fibrous materials such as textile fabrics, wood, non-wovens and paper.The fluorochemical composition is particularly useful for impartingstain release properties to a substrate that comprises natural fibers,in particular a substrate that consists of cellulose fibers or asubstrate consisting of cellulose and polyester fibers. Substratestreated with a fluorochemical composition of this invention haveparticular good stain release properties for dirty motor oil stains andtea stains.

In order to affect treatment of a textile substrate, the substrate canbe immersed in a diluted emulsion. The saturated substrate can then berun through a padder/roller to remove excess emulsion, dried and curedin an oven at a temperature and for a time sufficient to provide a curedtreated substrate. This curing process is typically carried out attemperatures between about 50° C. and 190° C. depending on theparticular system or application method used. In general, a temperatureof about 120° C. to 170° C., in particular of about 150° C. to 170° C.for a period of about 20 seconds to 10 minutes, preferably 3 to 5minutes, is suitable.

The invention is further illustrated by reference to the followingexamples without however the intention to limit the invention thereto.

EXAMPLES

Formulation and Treatment Procedure

Treatment baths were formulated containing a defined amount of thefluorochemical treatment agent. Treatments were applied to the testsubstrates by padding to provide a concentration of 0.3% or 0.6% solids(based on fabric weight and indicated as SOF (solids on fabric)) anddrying the samples at 150° C. during 3 minutes. The test substrates usedin the Examples were commercially available and are listed below:

* PES/CO: polyester/cotton 67/33 blends, available from Arlitex,Avelgem, Belgium.

* 100% cotton: available from UCO company, Destelbergen, Belgium

After drying, the substrates were tested for their stain release andrepellency properties.

Respective data of stain release, water and oil repellency shown in theExamples and Comparative Examples were based on the following methods ofmeasurement and evaluation criteria:

Stain Release Test

The stain release test was performed using two types of stains:

Dirty Motor Oil (DMO) obtained from General Motors Garage Houttequiet,Beveren; Belgium

Tea: obtained by immersing a Lipton™ yellow teabag in 165 ml at 65° C.for 3 minutes

Staining Procedure 1: Drop Method

10 cm×10 cm test samples were stained with 3 drops DMO or tea for PES/COor with 4 drops DMO or tea for cotton. The samples were equilibrated atroom temperature during 24 hours after which the degree of staining wasevaluated by measuring the difference in reflection of a stained versusunstained sample, using a Minolta color meter (Lamp D65). An average of3 measurements were done for each stain, resulting in a ΔL_(IN) value.

Staining Procedure 2: Brush Method

For this procedure, 0.35 ml DMO or 0.5 ml tea for PES/CO or 0.5 ml DMOor 0.6 ml tea for cotton were placed on 10 cm×10 cm test samples. Thestain was brushed into the fabric by brushing 3 times around in aplastic holder of 5 cm diameter placed around the staining liquid. Thereflection measurement was done as described above.

Laundering procedure

The test samples were pinned on a PES/CO ballast (total 3 kg) or acotton ballast (total 4 kg), and laundered in a Miele washing machinetype W 832. A commercial detergent (20 g/kg Clax 100 for PES/CO or Claxcrystal for cotton, available from Diversy Lever) was added and thesubstrates were washed at 70° C., using the main washing program,followed by four rinse cycles and centrifuging. The samples were driedin a tumble dryer and ironed at 150° C. for 15 seconds. Unstainedsamples were treated the same way. The samples were measured with theMinolta meter and compared to unstained samples, resulting in aΔL_(LD70° C.) value. The less negative value for ΔL_(LD70° C.) obtainedcompared to ΔL_(IN), the better the stain release properties were. %ΔΔL,calculated according to formula %ΔΔL=(ΔL_(IN)−ΔL_(LD70° C.)/ΔL_(IN))×100gave an indication of the percentage of stain removed during thelaundering process. The higher the value, the better the stain removal.

Water Repellency Test (WR)

The water repellency (WR) of a substrate was measured using a series ofwater-isopropyl alcohol test liquids and was expressed in terms of the“WR” rating of the treated substrate. The WR rating corresponded to themost penetrating test liquid which did not penetrate or wet thesubstrate surface after 15 seconds exposure. Substrates which werepenetrated by or were resistant only to 100% water (0% isopropylalcohol) test liquid, the least penetrating test liquid, were given arating of 0. Substrates resistant to test liquid which was 100%isopropyl alcohol (0% water), the most penetrating test liquid, weregiven a rating of 10. Other intermediate ratings were calculated bydividing the percent isopropylalcohol in the test liquid by 10, e.g., atreated substrate resistant to a 70%/130% isopropyl alcohol/water blend,but not to an 80%/20% blend, would be given a rating of 7.

Oil Repellency (OR)

The oil repellency of a substrate was measured by the AmericanAssociation of Textile Chemists and Colorists (AATCC) Standard TestMethod No. 118-1983, which test was based on the resistance of a treatedsubstrate to penetration by oils of varying surface tensions. Treatedsubstrates resistant only to Nujol® mineral oil (the least penetratingof the test oils) were given a rating of 1, whereas treated substratesresistant to heptane (the most penetrating of the test liquids) weregiven a rating of 8. Other intermediate values were determined by use ofother pure oils or mixtures of oils, as shown in the following table.

Standard Test Liquids AATCC Oil Repellency Rating Number Compositions 1Nujol ® 2 Nujol ®/n-Hexadecane 65/35 3 n-Hexadecane 4 n-Tetradecane 5n-Dodecane 6 n-Decane 7 n-Octane 8 n-Heptane

Abbreviations

The following abbreviations and trade names were used in the Examplesand Comparative Examples:

EtOAc: ethylacetate

RSH: 2-mercapto ethanol

AIBN: azo(bis)isobutyronitrile

HOEMA: 2-hydroxyethyl methacrylate

BA: butylacrylate

DIAA: diaceto acrylamide

MEFOSEA: N-methyl perfluorooctyl sulfonamido ethyl acrylate

PEG²⁰⁰⁻⁸⁰⁰⁰: polyethylene glycol, superscript number is indicative ofMw, available from Huls, Germany

IPA: isopropyl alcohol

TEA: triethylamine

GMA: glycidyl methacrylate (2,3-epoxypropyl methacrylate)

BO: 2-butanone oxime

IPDI: isophorone diisocyanate

DBTDL: dibutyltin dilaurate

MEHQ: methylhydroquinone

DESW : dicyclohexyl methane-4,4′-diisocyanate, available from Bayer(Germany) as DESMODUR™ W

DESN: aliphatic polyisocyanate, available from Bayer (Germany) asDESMODUR™ N

DESL: aromatic triisocyanate, available from Bayer (Germany) asDESMODUR™ L

Arquad T-50: tallow trimethyl ammonium chloride, available from Akzo,Littleborough, UK

PVA: polyvinyl alcohol

Mowiol™: polyvinyl alcohol with various weight average molecular weightsas indicated in the table, available from Hoechst

Mowiol ™ type Degree of hydrolysis Molecular weight Mowiol ™ 3-83 83 14000 Mowiol ™ 3-98 98  16000 Mowiol ™ 10-74 74  20000 Mowiol ™ 4-98 98 27000 Mowiol ™ 5-88 88  35000 Mowiol ™ 10-98 98  61000 Mowiol ™ 15-7979 100000 Mowiol ™ 20-98 98 125000 Mowiol ™ 18-88 88 130000 Mowiol ™28-98 98 145000 Mowiol ™ 26-88 88 160000 Mowiol ™ 40-88 88 205000

Polyvinyl™: polyvinyl alcohol, of various grades according to the table,available from Wacker-Chemie

Degree of Polyviol ™ type hydrolysis (mol %) Polyviol ™ V03/240 75-79Polyviol ™ V03/180 82-85 Polyviol ™ V03/140 86-89 Polyviol ™ G04/20 97.5-99.58 Polyviol ™ M05/290 69-73 Polyviol ™ M05/140 86-89 Polyviol ™W25/190 81-84 Polyviol ™ W25/100 90-93 Polyviol ™ W45/450 42-50

Culminal™ MHPC 50: Methylhydroxypropyl cellulose, available from Aqualon

Culminal™ MC25 PF: Methyl cellulose, available from Aqualon

Klucel™ M: Hydroxypropyl cellulose, with 2% Brookfield viscosity of 5000mPas., available from Aqualon

Klucel™ E: Hydroxypropyl cellulose with 2% Brookfield viscosity of 7mPas, available from Aqualon

Klucel™ L: Hydroxypropyl cellulose with 2% Brookfield viscosity 10 mPas,available from Aqualon

Nexton™ D-1200: hydrophobically modified hydroxyethyl cellulose,available from Aqualon

Nexton™ D-2500 W: hydrophobically modified hydroxyethyl cellulose with2% Brookfield viscosity of 25,000, available from Aqualon

Blanose™ CMC: sodium carboxymethyl cellulose, available from Aqualon

Cellulose gum 7L: sodium carboxymethyl cellulose, available from Aqualon

All parts, ratios, percentages etc. in the following examples are byweight unless otherwise noted.

A. Synthesis of Hydroxy Terminated Oligomers (HTO)

1. Synthesis of urethane acrylate HOEMA/IPDI/BO (molar ratio 1/1/1)

The urethane acrylate HOEMA/IPDI/BO (molar ratio 1/1/1), used in thepreparation of hydroxy terminated oligomers was prepared as follows:

A round bottom flask equipped with a mechanical stirrer, a temperaturecontrol, addition funnel, and nitrogen inlet and outlet, was chargedwith 111 g (0.5 moles) IPDI, 65 g (0.5 moles) HOEMA, 200 g EtOAc, 0.1 gphenotiazin, 0.1 g MEHQ and 0.2 g dibutyl tin dilaurate. The reactionmixture was slowly heated to about 50° C. A solution of 44 g (0.5 moles)2-butanone oxime, dissolved in 20 g EtOAc was added over a period of 1hour. Then the reaction mixture was stirred at 72° C. for 6 hours. IRanalysis indicated that all isocyanate groups had reacted.

2. Synthesis of hydroxy terminated oligomers (HTO)

Hydroxy terminated oligomers (HTO) of Table 1 were made using aprocedure similar to the synthesis of MEFOSEA/RSH 4/1 (indicated asHTO-1 in Table 1):

A round bottom flask equipped with two reflux condensers, a stirrer, atemperature control, a nitrogen inlet and a vacuo outlet was chargedwith 2.4 moles (1433 g) MEFOSEA and 987 g EtOAc. The mixture was heatedat 40° C. until all fluorochemical monomers were dissolved. 0.6 moles(46.8 g) 2-mercaptoethanol and 0.15% AIBN were added. The reactionmixture was gradually heated to 80° C. The reaction was run undernitrogen atmosphere at 80° C. for 16 hours, after which more than 95%conversion was obtained.

TABLE 1 Composition of Hydroxy Terminated Oligomers (HTO) Molar OligomerComposition Ratio HTO-1 MEFOSEA/RSH 4/1 HTO-2 MEFOSEA/RSH 8/1 HTO-3(HOEMA¹/IPDI¹/BO¹)/BA/RSH 1/3/1 HTO-4 BA/DIAA/RSH 4/1/1 HTO-5BA/DIAA/RSH 3/0.5/1 HTO-6 (HOEMA/IPDI/BO)/BA/RSH 3.5/0.5/1 HTO-7BA/GMA/RSH 4/1/1

B. Synthesis of fluorochemical compounds (FC)

Several of the fluorochemical compounds given in Table 2 were preparedusing a procedure similar to the synthesis of Desmodur W/HTO-1/PEG¹⁴⁵⁰(molar ratio 3/2/2) (FC-11 in Table 2):

A round bottom flask equipped with a condensor, thermometer, stirrer andnitrogen inlet was charged with 7.86 g (0.03 moles)Desmodur W, 29 g(0.02 moles) PEG¹⁴⁵⁰, 82.2 g (0.02 moles, 60% solids solution) HTO-1 and167 g ethyl acetate. The reaction mixture was heated to 50° C. afterwhich catalyst was added (TEA/SN-octanoate, available from Witco asFormez C-2). The temperature of the mixture was raised to 75° C. and thereaction was run until completion.

C. Emulsification

The fluorochemical compound obtained in step B (20 g solids) was addedto deionized water containing 1.2 g Arquad T-50 (50% solids) emulsifier.The mixture was homogenized using an ultrasonic probe (Branson 250sonifier) after which the organic solvent was removed under vacuum. Anemulsion containing 15% fluorochemical compound was obtained.

TABLE 2 Composition of FIuorochemical Urethanes (FC) Molar FCComposition of Fluorochemical Compound Ratio FC-1DESN/HTO-1/HTO-3/PEG¹⁰⁰⁰ 2/2/2/1 FC-2 DESN/HTO-1/HTO-3/PEG¹⁴⁵⁰ 2/2/2/1FC-3 DESN/HTO-1/HTO-3/PEG²⁰⁰⁰ 2/2/2/1 FC-4 DESN/HTO-1/HTO-3/PEG¹⁴⁵⁰3/2/3/2 FC-5 DESN/HTO-2/HTO-3/PEG¹⁴⁵⁰ 3/2/3/2 FC-6DESN/HTO-1/HTO-7/PEG¹⁰⁰⁰ 2/2/2/1 FC-7 DESN/HTO-1/HTO-4/PEG¹⁰⁰⁰ 2/2/2/1FC-8 DESN/HTO-1/HTO-5/PEG¹⁰⁰⁰ 2/2/2/1 FC-9 DESN/HTO-1/HTO-6/PEG¹⁰⁰⁰2/2/2/1 FC-10 DESL/HTO-1/PEG¹⁴⁵⁰/BO 3/2/2/3 FC-11 DESW/HTO-1/PEG¹⁴⁵⁰3/2/2 FC-12 DESW/HTO-1/PEG¹⁰⁰⁰ 3/2/2 FC-13 DESW/HTO-1/PEG⁸⁰⁰ 3/2/2 FC-14DESW/HTO-2/PEG¹⁰⁰⁰ 3/2/2 FC-15 DESW/HTO-2/PEG⁴⁰⁰⁰ 3/2/2 FC-16DESW/HTO-1/PEG⁴⁰⁰⁰ 3/2/2 FC-17 DESW/HTO-1/PEG⁸⁰⁰⁰ 4/2/3 FC-18DESW/HTO-1/PEG⁴⁰⁰⁰ 4/2/3 FC-19 DESW/HTO-1/PEG¹⁰⁰⁰ 6/2/5 FC-20DESW/HTO-1/HTO-3/PEG¹⁴⁵⁰ 3/1.5/0.5/2 FC-21 DESW/HTO-1/HTO-3/PEG¹⁰⁰⁰3/1.5/0.5/2 FC-22 DESW/HTO-1/HTO-7/PEG¹⁰⁰⁰ 3/1.5/0.5/2 FC-23DESW/HTO-2/HTO-3/PEG¹⁰⁰⁰ 3/1.5/0.5/2 FC-24 DESW/HTO-2/HTO-7/PEG¹⁰⁰⁰3/1.5/0.5/2 FC-25 DESW/HTO-2/HTO-3/PEG²⁰⁰⁰ 3/1.5/0.5/2 FC-26DESW/HTO-2/HTO-7/PEG²⁰⁰⁰ 3/1.5/0.5/2

Examples 1 to 7 and Comparative Example C-1

In Examples 1 to 7, fluorochemical compounds according to the inventionwere prepared and emulsified following the general procedure describedabove. Polyester/cotton (PES/CO) blends were treated with thefluorochemical compounds so as to give 0.3 or 0.6% SOF. After treatment,the fabrics were dried at 150° C. for 3 minutes. The treated PES/COsubstrates were stained with dirty motor oil using the drop method.Comparative Example C-1 was made with untreated PES/CO fabric. Theresults for stain release and oil and water repellency are given inTable 3.

TABLE 3 Stain Release (DMO-Drop) and Repellency Properties of TreatedPES/CO Fluoro- Initial Per- Stain Release Color Ex chemical % formanceMeasurement No Compound SOF OR WR ΔL_(IN) ΔL_(LD70°C.) % ΔΔL 1 FC-1 0.35 8 −5.88 −1.07 82 2 FC-6 0.6 6 8 −13.74 −8.35 39 3 FC-7 0.6 6 10  −3.26−1.23 62 4 FC-8 0.6 6 10  −6.48 −2.38 63 5 FC-9 0.3 4 5 −12.32 −6.7 46 6FC-10 0.6 5 4 −7.35 −3.27 56 7 FC-11 0.3 5 6 −5.63 −0.19 97 C-1 — — 0 0−15.45 −9.56 38

The results show that all fluorochemical compounds according to theinvention provided good to very good DMO stain release. In some cases(e.g., Example 7), no visible stain remained on the substrate afterlaundering. Furthermore, the fluorochemical compounds of the presentinvention not only provided the substrate with good stain release, butalso with good to high oil and water repellency which presents a furtheradvantage.

Examples 8 to 27 and Comparative Example C-2

In Examples 8 to 27, the same type of experiment was repeated but thistime the DMO was applied to the fabric by the brush method. ComparativeExample C-2 was made with untreated PES/CO fabric. The results of stainrelease and oil and water repellency are given in Table 4.

TABLE 4 Stain Release (DMO-Brush Method) and Repellent Properties ofTreated PES/CO Fluoro- Initial Per- Stain Release Color Ex chemical %formance Measurement No Compound SOF OR WR ΔL_(IN) ΔL_(LD70°C.) % ΔΔL  8FC-2 0.6 6 10  −18.31 −7.86 57  9 FC-3 0.3 6 10  −18.30 −9.02 51 10 FC-40.3 5 9 −18.52 −9.38 49 11 FC-5 0.3 5 6 −18.89 −10.17 46 12 FC-1I 0.6 610  −18.4 −5.56 70 13 FC-12 0.3 6 8 −18.53 −5.46 71 14 FC-13 0.6 6 9−18.35 −6.09 67 15 FC-14 0.6 6 4 −18.36 −6.59 64 16 FC-15 0.3 1 2 −17.26−7.45 57 17 FC-16 0.3 2 3 −17.27 −9.35 46 18 FC-17 0.3 1 0 −17.06 −10 4119 FC-18 0.6 4 1 −17.95 −8.36 53 20 FC-19 0.3 5 5 −18.84 −6 68 21 FC-200.3 3 5 −18.51 −8.3 55 22 FC-21 0.6 6 10  −17.81 −7.06 60 23 FC-22 0.6 610  −18.64 −4.07 78 24 FC-23 0.3 5 5 −18.57 −7.12 62 25 FC-24 0.3 5 4−18.53 −7.08 62 26 FC-25 0.3 2 2 −17.92 −7.59 58 27 FC-26 0.3 1 1 −17.55−7.7 56 C-2 — — 0 0 −15.32 −8.67 43

The results indicate that even in the more severe brush method, good DMOstain release was observed with treated fabric.

Examples 28 to 47 and Comparative Example C-3

In Examples 28 to 47, the same type of experiment as above was repeatedwith 100% cotton substrates treated with the fluorochemicalcompositions. According to the general procedure described above, DMOstain was applied to the cotton using the brush method. ComparativeExample C-3 was made with untreated cotton fabric. The results of stainrelease and oil and water repellency are given in Table 5.

TABLE 5 Stain Release (DMO-Brush Method) and Repellent Properties ofTreated Cotton Fluoro- Initial Per- Stain Release Color Ex chemical %formance Measurement No Compound SOF OR WR ΔL_(IN) ΔL_(LD70°C.) % ΔΔL 28FC-2 0.3 4 6 −19.55 −8.33 57 29 FC-3 0.3 3 6 −18.83 −8.71 54 30 FC-4 0.33 6 −19.65 −8.56 56 31 FC-5 0.3 2 3 −19.37 −8.76 55 32 FC-11 0.6 4 4−18.57 −8.74 53 33 FC-12 0.6 4 3 −18.68 −5.14 72 34 FC-13 0.6 6 7 −18.89−5.74 70 35 FC-14 0.6 5 4 −18.73 −4.26 77 36 FC-15 0.6 2 1 −19.65 −8.3458 37 FC-16 0.6 1 1 −18.25 −8.64 53 38 FC-17 0.6 2 2 −18.03 −8.85 51 39FC-18 0.6 2 1 −17.66 −8.78 50 40 FC-19 0.6 3 2 −18.59 −9.03 51 41 FC-200.6 3 4 −19.28 −8.37 57 42 FC-21 0.6 4 5 −18.87 −7.46 60 43 FC-22 0.6 57 −19.11 −4.04 79 44 FC-23 0.6 4 2 −19.18 −7.53 61 45 FC-24 0.6 3 3−19.12 −7.37 61 46 FC-25 0.6 2 1 −19.35 −8.25 57 47 FC-26 0.6 2 1 −19.42−8.45 56 C-3 — — 0 0 −15.70 −8.76 44

Even on cotton substrates, good percentage of stain removal (%ΔΔL) wasobserved for oily stains such as DMO.

Examples 48 to 54 and Comparative Example C-4

In Examples 48 to 54, PES/CO blends treated with the fluorochemicalcompounds according to the invention were stained with tea using thedrop method. Comparative Example C-4 was made with untreated fabric. Theresults of stain release and oil and water repellency are given in Table6.

TABLE 6 Stain Release (Tea-Drop Method) and Repellent Properties ofTreated PES/CO Initial Per- Stain Release Color Ex Fluorochemical %formance Measurement No Compound SOF OR WR ΔL_(IN) ΔL_(LD70°C.) % ΔΔL 48FC-1 0.6 6 9 −5.89 −0.81 86 49 FC-6 0.6 6 8 −5.82 −0.72 88 50 FC-7 0.6 610  −4.96 −0.41 92 51 FC-8 0.6 6 10  −6.3 −0.46 93 52 FC-9 0.6 5 7 −6.93−0.99 86 53 FC-10 0.3 3 4 −6.35 −0.97 85 54 FC-11 0.6 5 7 −8.84 −0.99 89C-4 — — 0 0 −2.32 −0.91 61

A high percentage of tea stain removal was observed.

Examples 55 to 74 and Comparative Example C-5

In Examples 55 to 74, PES/CO substrates treated with the fluorochemicalcompounds according to the invention were tested with tea stains, usingthe brush method. Comparative Example C-5 was made with untreatedmaterial. The results of stain release and oil and water repellency aregiven in Table 7.

TABLE 7 Stain Release (Tea-Brush Method) and Repellent Properties ofTreated PES/CO Initial Per- Stain Release Color Ex Fluorochemical %formance Measurement No Compound SOF OR WR ΔL_(IN) ΔL_(LD70°C.) % ΔΔL 55FC-2 0.6 6 10 −1.32 −0.77 42 56 FC-3 0.6 6 10  −1.6 −1 38 57 FC-4 0.3 59 −2.65 −1.1 58 58 FC-5 0.6 5 8 −1.87 −1.02 45 59 FC-11 0.6 6 10  −1.38−0.55 60 60 FC-12 0.6 6 8 −1.66 −0.79 52 61 FC-13 0.6 6 9 −1.5 −0.77 4962 FC-14 0.6 6 4 −I.52 −0.83 45 63 FC-15 0.6 3 3 −1.87 −0.78 58 64 FC-160.6 5 3 −2.45 −0.83 66 65 FC-17 0.6 4 1 −2.49 −0.82 67 66 FC-18 0.6 4 1−2.27 −0.68 70 67 FC-19 0.6 6 5 −2.31 −0.47 80 68 FC-20 0.6 4 5 −1.54−0.64 58 69 FC-21 0.6 6 10  −1.56 −0.67 57 70 FC-22 0.6 6 10  −1.81−0.82 55 71 FC-23 0.6 6 5 −1.76 −1.05 40 72 FC-24 0.6 5 5 −1.79 −0.98 4573 FC-25 0.6 3 4 −2.48 −0.95 62 74 FC-26 0.6 2 4 −2.18 −0.8 63 C-5 — — 00 −2.62 −1.22 53

Although in some cases the percentage stain removal for the tea stain ontreated substrates was not much better or even inferior than theuntreated samples, all treated samples showed a much less negative valuefor ΔL_(LD70° C.) than the untreaed sample. This indicates that thestain remaining on treated substrate was less visible after laundering.

Examples 75 to 94 and Comparative Example C-6

In Examples 75 to 94, treated cotton substrates were stained with teausing the brush method. Comparative Example C-6 was made with untreatedmaterial. The results of stain release and oil and water repellency aregiven in Table 8.

TABLE 8 Stain Release (Tea-Brush Method) and Repellent Properties ofTreated Cotton Initial Per- Stain Release Color Ex Fluorochemical %formance Measurement No Compound SOF OR WR ΔL_(IN) ΔL_(LD70°C.) % ΔΔL 75FC-2 0.3 4 6 −2.33 −0.66 72 76 FC-3 0.3 3 6 −2.52 −0.42 83 77 FC-4 0.3 36 −2.17 −0.72 67 78 FC-5 0.3 2 3 −2.38 −0.89 63 79 FC-11 0.6 4 4 −2.02−0.36 82 80 FC-12 0.6 4 3 −2.06 −0.39 81 81 FC-13 0.6 6 7 −2.41 −0.39 8482 FC-14 0.6 5 4 −2.5 −0.6 76 83 FC-15 0.6 2 1 −2.93 −0.78 73 84 FC-160.6 1 1 −2.66 −0.92 65 85 FC-17 0.6 2 2 −2.52 −1.06 58 86 FC-18 0.6 2 1−2.64 −0.97 63 87 FC-19 0.6 3 2 −2.05 −0.58 72 88 FC-20 0.6 3 4 −2.82−0.6 79 89 FC-21 0.6 4 5 −2.3 −0.36 84 90 FC-22 0.6 5 7 −2.52 −0.43 8391 FC-23 0.6 4 2 −2.84 −0.47 83 92 FC-24 0.6 3 3 −2.43 −0.42 83 93 FC-250.6 2 1 −3.03 −0.56 82 94 FC-26 0.6 2 1 −3.03 −0.63 79 C-6 — — 0 0 −3.21−1.36 58

The results show that cotton fabric treated with the fluorochemicalcompounds of the invention showed high tea stain removal. Also medium tohigh water and oil repellency properties were obtained.

Examples 95 to 103 and Comparative Example C-7

Examples 95 to 103, PES/CO substrate was treated with fluorochemicalcompound FC-19 (Example 95) or with a 50/50 blend of FC-19 with thepolyvinyl alcohols listed in Table 9 (Examples 96 to 103). The substratewas treated in such a way as to have 0.6% SOF fluorochemical compoundand 0.6% SOF polyvinyl alcohol (except Example 95). Comparative ExampleC-7 was made using untreated PES/CO. The treated and untreatedsubstrates were stained with DMO (brush method) and tested for theirstain release and repellency properties. The results are given in Table9.

TABLE 9 Stain Release for DMO Stains Initial Per- Stain Release Color Exformance Measurement* No PVA OR WR ΔL_(IN) ΔL_(LD70°C.) % ΔΔL  95 — 6 1−55.8 −6.6 88  96 Mowiol ™ 3-83 6 1 −58.4 −4.2 93  97 Mowiol ™ 3-98 6 1−59.7 −8.0 87  98 Mowiol ™ 10-74 6 1 −59.3 −4.5 92  99 Mowiol ™ 5-88 6 1−58.8 −5.9 90 100 Mowiol ™ 15-79 6 1 −59.5 −5.8 90 101 Mowiol ™ 18-88 61 −59.3 −5.2 91 102 Mowiol ™ 26-88 6 1 −59.8 −3.4 94 103 Mowiol ™ 40-886 1 −59.2 −4.8 92 C-7 — 0 0 −45.0 −21.9 51 Note: *lens opening of theMinolta colorimeter was set at 53 mm

The data shows that the high stain release properties provided by thefluorochemical compositions can improved by the addition of polyvinylalcohol without sacrificing oil and water repellent properties. Theinfluence of polyvinyl alcohol is reflected by a less negativeΔL_(LD70° C.) value, indicating better stain release properties.

Examples 104 to 115 and Comparative Examples C-8 and C-9

In Examples 104 to 115, PES/CO substrate was treated with fluorochemicalcompound FC-19 at various add-on levels with and without the addition ofMowiol™ 3-83 as described in Table 10. Comparative Example C-8 was madeusing untreated substrate and Comparative Example C-9 was made withPES/CO substrate treated with Mowiol™ 3-83 alone (1% SOF). The treatedand untreated substrates were stained with DMO (brush) and tested fortheir stain release and oil and water repellency properties. The resultsare given in Table 10.

TABLE 10 % Initial Per- Stain Release Color Ex % Mowiol ™ formanceMeasurement* No FC-19 3-83 OR WR ΔL_(IN) ΔL_(LD70°C.) % ΔΔL 104 0.6 — 60 −16.9 −1.5 91 105 0.6 1.0 6 4 −16.5 −0.4 98 106 0.6 0.6 6 1 −16.7 −0.895 107 0.6 0.4 6 3 −16.8 −1.6 90 108 0.4 — 6 4 −17.0 −2.3 87 109 0.4 1.06 0 −16.6 −0.8 95 110 0.4 0.6 6 0 −17.0 −1.9 89 111 0.4 0.4 6 0 −16.7−0.7 96 112 0.3 — 5 1 −17.2 −3.6 79 113 0.3 1.0 5 1 −16.3 −1.7 90 1140.3 0.6 5 0 −16.6 −1.0 94 115 0.3 0.4 5 0 −17.0 −2.2 87 C-8 — — 0 0−14.2 −8.5 40 C-9 — 1.0 0 0 −15.1 −5.8 62 Note: *lens opening of theMinolta colorimeter was set at 53 mm

The results demonstrate that addition of polyvinyl alcohol to thefluorochemical composition improves the stain release performance.Additionally, it can be seen that part of the fluorochemical treatingagent can be replaced by polyvinyl alcohol while maintaining the highlevel of stain release properties.

Examples 116 to 125 and Comparative Example C-10

In Examples 116 to 125, PES/CO substrate was treated with fluorochemicalcompound FC-19 (Example 116) or with a 50/50 blend of FC-19 with variousPolyvinyl™ type polyvinyl alcohols (Examples 117 to 125). The substratewas treated in such a way as to have 0.6% SOF fluorochemical compoundand 0.6% SOF polyvinyl alcohol. Comparative Example C-10 was made usinguntreated PES/CO. The treated and untreated substrates were stained withDMO (brush) and tested for their stain release and repellencyproperties. The results are given in Table 11.

TABLE 11 Initial Stain Release Color Ex Performance Measurement* NoPolyviol ™ OR WR ΔL_(IN) ΔL_(LD70°C.) % ΔΔL 116 — 6 1 −55.8 −6.6 88 117V03/240 6 0 −59.9 −2.8 95 118 V03/180 6 0 −58.9 −4.2 93 119 V03/140 6 1−58.6 −2.9 95 120 G04/20 6 0 −58.8 −5.1 91 121 M05/290 6 2 −56.9 −5.4 90122 M05/140 6 0 −59.9 −3.1 95 123 W25/190 6 0 −57.7 −2.5 96 124 W25/1006 0 −59.1 −3.0 95 125 W45/450** 6 2 −59.2 −4.7 92 C-10 — 0 0 −45.0 −21.951 Note: *lens opening of Minolta colorimeter was set at 53 mm**Polyviol ™ W45/450 was not soluble in water and had to be dissolved inIPA/Water 1/1

In this case, the same observations were made as with the Mowiol™ typepolyvinyl alcohols.

Examples 126 to 137 and Comparative Examples C-11 and C-12

In Examples 126 to 137, PES/CO substrate was treated with fluorochemicalcompound FC-19 or with a 50/50 blend of FC-19 with polyvinyl alcohol, asgiven in Table 12. The substrate was treated in such a way as to have0.6% SOF fluorochemical compound or 0.6% SOF fluorochemical compound and0.6% SOF polyvinyl alcohol. Comparative Examples C-11 and C-12 were madeusing untreated PES/CO. The treated and untreated substrates werestained with tea or wine and tested for their stain release andrepellency properties. The results are give in Table 12.

TABLE 12 Initial Per- Stain Release Ex formance Performance* NoPolyvinylalcohol OR WR ΔL_(IN) ΔL_(LD70°C.) % ΔΔL Stain: TEA 126 — 6 1−6.8 −1.7 75 127 Mowiol ™ 3-83 6 1 −6.5 −1.6 75 128 Mowiol ™ 5-88 6 0−7.1 −1.7 76 129 Airvol ™ 165 1 0 −6.7 −1.2 82 130 Polyviol ™ V03/180 61 −6.6 −1.5 77 131 Polyviol ™ W25/190 6 4 −6.9 −1.8 75 C-11 — 0 0 −6.3−3.4 46 Stain: WINE 132 — 6 1 −14.7 −1.7 89 133 Mowiol ™ 3-83 6 1 −14.1−1.6 88 134 Mowiol ™ 5-88 6 0 −15.3 −1.5 90 135 Airvol ™ 165 1 0 −13.3−0.7 95 136 Polyviol ™ V03/180 6 1 −15.1 −1.3 91 137 Polyviol ™ W25/1906 4 −16.7 −1.8 89 C-12 — 0 0 −13.4 −3.5 74 Note: *lens opening of theMinolta colorimeter was set at 53 mm instead of 18 mm

The results in Table 12 show that, in some cases, the addition of apolyvinyl alcohol the fluorochemical composition of the inventionresults in a slightly improved stain release performance with respect toaqueous based stains such as tea and wine.

Examples 138 to 145

In Examples 138 to 145, PES/CO substrate was treated with fluorochemicalcompounds FC-13 or FC-16 or with a 50/50 blend of the fluorochemicalcompound and polyvinyl alcohol Mowiol™ 3-83. The substrate was treatedin such a way as to have 0.6% fluorochemical compound and 0.6% SOFpolyvinyl alcohol. The treated substrates were stained with tea or DMO(brush) and tested for their stain release and oil and water repellencyproperties. The results are given in Table 13.

TABLE 13 Stain Release For Tea and DMO Stains FC Initial Per- StainRelease Color Ex Com- formance Measurement No pound PVA OR WR ΔL_(IN)ΔL_(LD70°C.) % ΔΔL Stain: TEA 138 FC-13 — 6 0 −2.5 −0.9 65 139 FC-13Mowiol ™ 6 0 −2.6 −0.7 75 3-83 140 FC-16 — 4 0 −2.2 −0.5 79 141 FC-16Mowiol ™ 4 0 −2.1 −0.5 78 3-83 Stain: DMO 142 FC-13 — 6 0 −16.7 −5.6 67143 FC-13 Mowiol ™ 6 0 −16.4 −3.1 81 3-83 144 FC-16 — 4 0 −17.8 −8.3 53145 FC-16 Mowiol ™ 4 0 −17.5 −0.9 61 3-83

Also in this case, improved stain release performance were obtained byblending polyvinyl alcohol with the fluorochemical compound especiallyfor DMO stains.

Examples 146 to 167

Examples 146 to 167, PES/CO substrate was treated with fluorochemicalcompounds FC-13, FC-16 or FC-19 or with a 50/50 blend of thefluorochemical compound with cellulose derivatives, as given in Table14. The substrate was treated in such a way as to have 0.6% SOFfluorochemical compound or 0.6% SOF fluorochemical compound and 0.6% SOFcellulose derivative. The treated substrates were stained with tea orDMO (brush) and tested for their stain release and repellencyproperties. The results are given in Table 14.

TABLE 14 FC Initial Per- Stain Release Color Ex Com- Cellulose formanceMeasurement No pound Derivative OR WR ΔL_(IN) ΔL_(LD70°C.) % ΔΔL Stain:DMO 146 FC-13 — −16.7 −5.6 67 147 FC-13 Culminal ™ 6 0 −16.0 −3.1 81MHPC 50 148 FC-13 Klucel ™ M −16.4 −3.8 77 149 FC-16 — −17.8 −8.3 53 150FC-16 Culminal ™ 5 0 −16.4 −3.8 77 MHPC 50 151 FC-16 Klucel ™ M 4 1−16.4 −2.8 83 152 FC-19 — −17.1 −2.3 87 153 FC-19 Culminal ™ 6 0 −16.6−1.2 93 MHPC 50 154 FC-19 Culminal ™ 6 1 −16.4 −1.0 94 MC25 PF 155 FC-19Klucel ™ M 6 1 −16.9 −1.4 92 156 FC-19 Klucel ™ E 6 1 −17.1 −1.4 92 157FC-19 Klucel ™ L 6 1 −17.2 −1.5 91 158 FC-19 Nexton ™ 0 0 −15.3 −6.1 61D-1200 159 FC-19 Nexton ™ 3 0 −16.3 −5.3 68 D-2500W 160 FC-19 Blanose ™0 0 −15.4 −5.5 64 CMC 7LD 161 FC-19 Cellulose 1 0 −16.1 −5.8 64 Gum 7LStain: TEA 162 FC-13 — −2.5 −0.9 65 163 FC-13 Culminal ™ 6 0 −2.5 #0.868 MHPC 50 164 FC-13 Klucel ™ M −2.8 −1.1 60 165 FC-16 — −2.2 −0.5 79166 FC-16 Culminal ™ 5 0 −3.0 −1.0 68 MHPC 50 167 FC-16 Klucel ™ M 4 1−3.0 −1.0 68

The data shows that the addition of non-ionic cellulose ethers to thefluorochemical composition of the invention also improves the stainrelease performance of the fluorochemical composition. However, thenon-ionic cellulose either NEXTON™, which is a hydrophobically modifiedcellulose ether, resulted in a decrease of the stain releaseperformance. Also, the ionic cellulose derivatives resulted in a reducedstain release performance relative to a fluorochemical composition thatdid not include these ionic celluloses.

Examples 168 to 197

In Examples 168 to 197, PES/CO substrate was treated with fluorochenicalcompounds FC-13, FC-16 or FC-19 or with a 50/50 blend of thefluorochemical compound with polyethyleneglycol of various molecularweight, as given in Table 15. The fluorochemical compound and thepolyethyleneglycol (when used) were applied at 0.6% SOF each. Thetreated substrates were stained with DMO or tea and tested for theirstain release properties.

TABLE 15 Stain Release Color Ex Measurement* No FC PEG ΔL_(IN)ΔL_(LD70°C.) % ΔΔL Stain: DMO 168 FC-13 — −58.4 −13.6 77 169 FC-13 PEG200 −59.4 −11.2 81 170 FC-13 PEG 1000 −58.4 −11.8 80 171 FC-13 PEG 2000−57.9 −9.5 84 172 FC-13 PEG 4000 −58.4 −8.8 85 173 FC-16 — −54.3 −21.960 174 FC-16 PEG 200 −56.6 −21.9 61 175 FC-16 PEG 1000 −56.8 −19.7 65176 FC-16 PEG 2000 −55.1 −20.7 62 177 FC-16 PEG 4000 −56.2 −20.6 63 178FC-19 — −52.3 −6.9 87 179 FC-19 PEG 200 −53.9 −6.0 89 180 FC-19 PEG 1000−55.6 −6.8 88 181 FC-19 PEG 2000 −55.6 −6.5 88 182 FC-19 PEG 4000 −56.7−7.2 87 Stain: TEA 183 FC-13 — −6.5 −2.9 55 184 FC-13 PEG 200 −7.5 −4.441 185 FC-13 PEG 1000 −7.2 −3.5 51 186 FC-13 PEG 2000 −7.1 −3.6 49 187FC-13 PEG 4000 −6.2 −2.6 58 188 FC-16 — −6.2 −2.7 56 189 FC-16 PEG 200−5.9 −2.7 54 190 FC-16 PEG 1000 −5.8 −2.5 57 191 FC-16 PEG 2000 −5.8−2.7 53 192 FC-16 PEG 4000 −5.4 −2.4 56 193 FC-19 — −6.6 −1.9 71 194FC-19 PEG 200 −6.8 −2.0 71 195 FC-19 PEG 1000 −7.1 −2.0 72 196 FC-19 PEG2000 −7.3 −2.2 70 197 FC-19 PEG 4000 −5.6 −2.2 61 Note: *lens opening ofthe Minolta colorimeter was set at 53 mm

The results in Table 15 show that there is some improvement of the stainrelease performance of the fluorochemical composition when polyglycolsare added to the fluorochemical composition.

What is claimed is:
 1. A method for preparing a fluorochemicalcomposition comprising a polyurethane by reacting: (A) fluorochemicaloligomer of formula (I) M^(f) _(m)M_(n)—-Q¹—T¹  (I) wherein: M^(f)_(m)M_(n) represents fluorochemical oligomer comprising m units derivedfrom fluorinated monomers and n units derived from fluorine-freemonomers and wherein the fluorinated monomers and fluorine-free monomersmay be the same or different; m represents a value of 2 to 40; nrepresents a value of 0 to 20; T¹ is —OH or —NH₂; Q¹ and T¹ togetherrepresent an organic residue obtained by removing a hydrogen atom from achain transfer agent that is functionalized with T¹; and (B)difunctional compound reactive with an isocyanate and comprising apoly(oxyalkylene)group having 18 to 280 oxyalkylene moieties; with (C)diisocyanate or triisocyanate.
 2. A method according to claim 1, whereinsaid method for preparing said fluorochemical composition furthercomprises reacting with an isocyanate blocking agent or a fluorine-freeoligomer reactive with an isocyanate.
 3. A method according to claim 1,wherein said fluorinated monomers correspond to the following formula:R_(f)—L¹—E wherein: R_(f) is selected from the group consisting ofperfluorinated or partially fluorinated aliphatic groups; L¹ representsan organic divalent linking group; and E represents a free radicalpolymerizable group.
 4. A method according to claim 3, wherein E is anacrylate or a methacrylate group and L¹ is selected from the groupconsisting of alkylenes, poly(oxyalkylenes) having 1 to 4 oxyalkylenemoieties, and organic divalent linking groups according to the followingformula:

wherein: R³ is selected from the group consisting of linear or branchedalkylenes having 2 to 4 carbon atoms; and R⁴ represents an alkyl grouphaving 1 to 4 carbon atoms.
 5. A method according to claim 1, wherein Q¹corresponds to the formula: —S—R— wherein: R represents an organicdivalent linking group selected from the group consisting of linear orbranched alkylenes, cyclic alkylenes and arylenes.
 6. A method accordingto claim 1, wherein said difunctional compound used to prepare saidfluorochemical composition corresponds to the following formula:H—W¹—R⁶—(O—R⁷)_(i)—(O—R⁸)_(j)—W²—H wherein: R⁶ is selected from thegroup consisting of linear or branched alkylenes having 1 to 4 carbonatoms; R⁷ and R⁸ are each independently selected from the groupconsisting of linear or branched alkylenes having 2 to 4 carbon atoms;W¹ is selected from the group consisting of O, S and NH; W² is selectedfrom the group consisting of O, S and NH; i is an integer of 0 to 150; jis an integer of 0 to 150; and i+j is at least
 8. 7. A fluorochemicalcomposition obtained by the method of claim
 1. 8. A fluorochemicalcomposition comprising: (i) polyurethane obtained by reacting: (A)fluorochemical oligomer of formula (I) M^(f) _(m)M_(n)—Q¹—T¹  (I)wherein: M^(f) _(m)M_(n) represents a fluorochemical oligomer comprisingm units derived from fluorinated monomers and n units derived fromfluorine-free monomers and wherein the fluorinated monomers andfluorine-free monomers may be the same or different; m represents avalue of 2 to 40; n represents a value of 0 to 20; T¹ is —OH or —NH₂; Q¹and T¹ together represent an organic residue obtained by removing ahydrogen atom from a chain transfer agent that is functionalized withT¹; and (B) difunctional compound reactive with an isocyanate andcomprising a poly(oxyalkylene)group; with (C) diisocyanate ortriisocyanate; and (ii) polymer selected from the group consisting ofpolyvinyl alcohols, copolymers of (meth)acrylic acid and alkyl esters of(meth)acrylic acid, polyethylene glycols, and non-ionic cellulose etherswherein the ratio of said polyurethane (i) to said polymer (ii) is from1:0.6 to 1:2.5.
 9. A fluorochemical composition according to claim 8,wherein said reaction further comprises the step of reacting with anisocyanate blocking agent or a fluorine-free oligomer reactive with anisocyanate.
 10. A fluorochemical composition according to claim 8,wherein said difunctional compound corresponds to the following formula:H—W¹—R⁶—(O—R⁷)_(i)—(O—R⁸)_(j)—W²—H wherein: R⁶ is selected from thegroup consisting of linear or branched alkylenes having 1 to 4 carbonatoms; R⁷ and R⁸ are each independently selected from the groupconsisting of linear or branched alkylenes having 2 to 4 carbon atoms;W¹ is selected from the group consisting of O, S and NH; W² is selectedfrom the group consisting of O, S and NH; i is an integer of 0 to 150; jis an integer of 0 to 150; and i+j is at least
 8. 11. A method oftreatment of a substrate comprising the step of contacting saidsubstrate with a fluorochemical composition according to claim
 7. 12. Asubstrate comprising on at least part of at least one surface afluorochemical composition according to claim
 7. 13. The method of claim11 wherein said fluorochemical composition comprises a polyurethaneobtained by reacting: (A) fluorochemical oligomer of formula (I) M^(f)_(m)M_(n)—Q¹—T¹  (I) wherein: M^(f) _(m)M_(n) represents fluorochemicaloligomer comprising m units derived from fluorinated monomers and nunits derived from fluorine-free monomers and wherein the fluorinatedmonomers and fluorine-free monomers may be the same or different; mrepresents a value of 2 to 40; n represents a value of 0 to 20; T¹ is—OH or —NH₂; Q¹ and T¹ together represent an organic residue obtained byremoving a hydrogen atom from a chain transfer agent that isfunctionalized with T¹; and (B) difunctional compound capable ofreacting with an isocyanate and comprising a poly(oxyalkylene)group;with (C) diisocyanate or triisocyanate.
 14. The method of claim 11wherein said substrate is a fibrous substrate.
 15. The method of claim14 wherein said substrate comprises natural fibers.
 16. The method ofclaim 14 wherein said substrate is fibrous and said fibers are selectedfrom the group consisting of cellulose fibers, polyester fibers andblends thereof.
 17. The method of claim 16, wherein said fluorochemicalcomposition is used in amounts sufficient to provide 0.01 to 5 weightpercent of said fluorochemical composition on said substrate.
 18. Anemulsion comprising the composition of claim 7 further comprising water,and a surfactant in an amount sufficient to stabilize the emulsion. 19.The emulsion of claim 8, comprising 100 parts by weight fluorochemicalcomposition, 70 to 2000 parts by weight water and 1 to 25 parts byweight surfactant.